Cross-linked copolymer acrylonitrile fibers or films

ABSTRACT

Cross-linked acrylic fibers or films which are of improved hot water-resistance and have a silky hand or feel, are obtained by (i) preparing an acidic solution of a copolymer obtained by copolymerizing in an acidic medium (a) a vinyl monomeric material consisting mainly of acrylonitrile and (b) a polymerizable unsaturated monomer having a halogenated s-triazinyl group or halogenated pyrimidinyl group in the presence of (c) a polymerizable unsaturated monomer having a group containing active hydrogen, a group capable of forming active hydrogen, a pyridyl group, a pyrazinyl group or quinolyl group, and/or (d) protein, and then (ii) extruding a very stable acidic solution of the resulting polymer into the form of fibers or films, and then heat-treating. The obtained fibers, for example, are useful in making woven or knitted fabrics of correspondingly superior properties.

United States Patent Yamamoto et al. Nov. 5, 1974 [54] CROSS-LINKEDCOPOLYMER 3,478,006 ll/l969 Filling 260/85.5

ACRYLONITRILE FIBERS OR FILMS [75] Inventors: Akira Yamamoto; KunioNakaoji;

Kunio Oohara; Zendiro Momiyama; Primary ExammerStanford M. Levm HeiichimMurakami; Akira Tomita, Attorney, Agent, or Firm-Wenderoth, Lind &Ponack all of Otsu, Japan [73] Assignee: Toyo Boseki Kabushiki Kaisha[21] Appl. No.: 274,207

Related U.S. Application Data Cross-linked acrylic fibers or films whiclare of im- [62] Division of Ser. No. l66,3l3, July 26, 1971, Pat. No.Proved hot have 3,759,849, which is a division of Ser. No. 753,515,feel, are Obtamed y Preparing an ac1d1c solut1on Aug 19, 1963, P y 3 2,049, of a copolymer obtained by copolymerizing in an acidic medium (a)a vinyl monomeric material con- [30] Foreign Application Priority Datasisting mainly of acrylonitrile and (b) a polymerizable Sept. 2 1967Japan 42-56502 unsaturated monomer having a halogenated s'mazinyl Dec.25 1967 Japan 42-82509 group or halogenated pyrlmidlnyl group in Presence of (c) a polymerizable unsaturated monomer [52] U.S. Cl 260/80.72,260/8, 260/ 17.4, havmg a p l ng active hydrogen, a group 2 0mg]260/883, 264/182, 264M815 capable of formmg active hydrogen, a pyridylgroup, a 264/184 264/202 264/205, 264/206, pyrazmyl group or qumolylgroup, and/or (d) protem, 264/210, 264/236 and then (11) extrudmg a verystable ac1d1c solut1on of 51] Int. Cl. C08f19/00 the resulting Polymerinto the form of fibers of films, 58 Field of Search 260/80.72 79.7 andfiat-treating The Obtained fibers for exam ple, are useful in makingwoven or knitted fabrics of [56] References Cited correspondinglysuperior properties.

' UNITED STATES PATENTS 2,687,400 8/1954 DAlelio 260/78 1 Claim, 2Drawing Figures PATENTEUNUY 5 m4 3346386 STRENGTH (g/d) ELONGATION FIGZSTRENGTH /d) 02o'4'oe'o 8'o ELONGATION (Z) CROSS-LINKED COPOLYMERACRYLONITRILE FIBERS OR FILMS This application is a division ofapplication Ser. No. 166,313, filed July 26, 1971, now US. Pat. No.3,759,849, which in turn is a division of application Ser. No. 753,515,filed Aug. 19, 1968, now US. Pat. No. 3,626,049.

This invention relates to improved acrylic fibers and films high in thehot water-resistance, and also to processes for producing the same.

Generally fibers of acrylonitrile polymers have the disadvantage thatthey are much lower in strength and dimensional stability under heat,particularly in hot wa* ter, than any other synthetic fibers. Theresearches so far made to modify acrylic fibers have been directedmostly to the improvement of the dyeability and preventing offibrillation by copolymerizing acrylonitrile with other monomer(s).Therefore, sucm modification has resulted in the reduction of themolecular chain orientation of the acrylic fibers and also in thedeterioration in the hot water-resistance of the fibers.

There has recently been an attempt to improve the hot water-resistanceof acrylic fibers by introducing a cross-linkage between the moleculesof acrylic fibers. For example, in US. Pat. No. 3,399,007, there isdisclosed a process wherein a cross-linkable monomer such asdivinylbenzene is copolymerized with acrylonitrile. However, most ofsuch cross-linkable comonomers have the disadvantage that thecross-linking reaction proceeds so quickly during the polymerizing stepand up to the fiber formation step, that the polymer solution forforming shaped articles increases in viscosity or gels and the shapingoperation becomes difficult.

An object of the present invention is to provide fibers and films ofnovel cross-linked acrylonitrile copolymers high in hot water-resistanceand a process for producing the same. I

A further object of the present'invention is to provide improvedprotein-acrylonitrilegraft copolymer fibers and films having a silkyhand or feel and high in hot water-resistance.

A stil further object of the present invention is to provide a verystable solution for forming cross-linked acrylic fibers or films.

Other objects of the present invention will become clear from thefollowing descriptions which will be made partly by referring to theaccompanying drawings wherein:

FIG. 1 is a graph showing the relation between the elongation and thestrength of fibers of this invention as compared with conventionalfibers, and

FIG. 2 is a graph similar to FIG. 1 but showing the same relation inrespect of other fibers of this invention as compared with theconventional fibers.

These objects of the present invention maybe accomplished by preparingan acidic solution ofa copolymer obtained by copolymerizing in an acidicmedium (a) a vinyl monomeric material consisting mainly of acrylonitrileand (b) a polymerizable unsaturated monomer having a halogenateds-triazinyl group or halogenated pyrimidimyl group in the presence of(c) a polymerizable unsaturated monomer having a group containing activehydrogen, a group capable of formingactive hydrogen, a pyridyl group, apyrazinyl group or quinoyl group, and/or (d) protein, and then extrudingan acidic solution of the resulting polymer in the form of fibers orfilms, and then heat-treating.

The vinyl monomeric. material consisting mainly of acrylonitrile in thepresent invention include acrylonitrile alone or a mixture ofacrylonitrile and vinyl monomer(s) copolymerizable with acrylonitrile.Said vinyl monomers are, of course, other than those of the (b) and (c)monomers. In a monomeric mixture, acrylonitrile must be contained in anamount of at least percent by weight.

Examples of vinyl monomers are acrylic acid and methacrylic, theiresters such as methyl acrylate, methyl methacrylate and ethylacrylate,their amide derivatives such as acrylamide and methacrylamide,methacrylonitrile, allyl chloride, allyl sulfonic acid and its salts,ethylene sulfonic acid and its salts, itaconic acid and its esterderivatives, fumaronitrile, vinyl'ethers such as methyl vinyl ether andethyl vinyl ether, methyl vinyl ketone, styrene, a-substituted styrenessuch as a-methyl styrene, nucleus-substituted styrenes such as 0-, morp-methyl styrene, styrene sulfonic acid and its salts, vinyl esters suchas vinyl chloride and vinyl acetate, vinyl lactams such as vinylcaprolactam and vinyl pyrrolidone and vinyl imidazole.

The halogenated s-triazinyl group or halogenated pyrimidinyl group inthe polymerizable unsaturated monomer (hereinafter referred to asmonomer A) having a halogenated s-triazinyl group or halogenatedpyrimidinyl group is of the following structure: halogenated s-triazinylgroup halogenated pyrimidiny-l' group [wherein each of X and X is ahalogen, hydrogen, alkyl group, amino group, hydroxyl group, mercaptogroup, carboxyl group and wherein at least one of X and X must be ahalogen].

Examples of preferable monomers A are of the following structuralformulas:

2-a1ly1amino-4,6-dichloro s-triazine,

2-am'ino-'4 -allyoxy 6-chloro-s-triazine,

2-(p-vinylanilino)-4,6-dichloro-s-triazine,

2-acryloyloxyethylene amino-4,6-dichloro-s-triazine,

2-vinyloxyethylene amino-4,o-dichloro-s-triazine,

il i

and 2-(p-vinylphenoxy)-4,6-dichloro-s-triazine.

In the above formulas, R represents hydrogen or an alkyl group.

Further, those compounds in which the halogenated s-triazinyl group inthe above mentioned compounds substituted with a halogenated pyrimidinylgroup may also be used. Further, it is preferable that both X, and X inthe monomer A are halogens. Particularly, among the halogens, chlorineis preferable.

The most preferable examples of the monomer A are2-allylamino-4,o-dichloro-s-triazine, 2-amino-4allyloxy-o-chloro-s-triazine, 2-(p-vinylanilino)-4,6-dichloropyrimidine and 2-allylamino-4,6- dichloropyrimidine.

It is preferable that the content of the monomer A in the resultingacrylic copolymer is 0.03 to percent by weight, and more preferably 0.3to 5 percent by weight. In case the content of the monomer A componentis lower than the above mentioned range, the hot waterresistance of theobtained fibers and films can not be improved to a desirable degree. Onthe contrary, in case it is higher than the above mentioned range", theelongation and softness properties in the dry state of the thus-obtainedfibers and films are reduced.

Preferable examples of the polymerizable unsaturated monomer(hereinafter referred to as monomer B) having a group containing activehydrogen, a group capable of forming active hydrogen, a pyridyl group, apyrazinyl group or a quinolyl group are as follows:

All ylamlne OHQ=CHCH2NH2 Methallylamme CHz=C (CH5) CHzNHzAllylmethylamine- CH2=CHCH2NHCH3 Allylethylamine CH1=CHCH2NHCHCH3l-gli-egaylaminm- CHz=CHCH CHzNHCHzCH u ne.

B-Aminoethyl acrylatet CHZZC HCOOCHzCHrNH':

4-pentene-2-ol CH2=CHCHzCH (OH) CH3 fiHydroxyethylacrylate C Hz=C HO O OCHzCHO H B-Hydroxyethyl meth- CHz=C (CH3) 0 O 0 CHzCHz CH aerylate.Glycidy1methacrylate..-- CHz=C (CH3) 0 O O CH2CHCH2 Glycidyl acrylate OHz=CHC O 0 01120 370 Hz 2,3-dihydroxypropyl CH2=C (CH3) COOCH2OH OI-DCHzOH methacrylate.

Ethylene glycol mono- CH2=OHOCH2CHOH vinyl ether.

Dlethylene glycol mono- CH2=CH0 CHzCHzO CHzCHzOH vinyl ether.

lo-methacryloyl-p glucose CHzOH V H 3-o-methacryloyl-D-glucose6:o:methacryloylD-glucose 6-o-methacryloyl-D-galactose Z-N-methacryloylglucosamine CHIOH H CH l-acrylamidol -dioxy-gluciton l-o-p-vinylphenylglucose .c rnbir V Vinyl pyridine 2-methyl-5-vinyl pyridine 2-vinylquinoline and Vinyl pyrazine Of course, the monomers B are not limitedto the 6 Particularly preferable among the monomers B are allylamine,allyl alcohol and vinyl pyridine.

It is preferable that the content of the monomer B in the resultingacrylic copolymer is 0.3 to 10 percent by weight, and more preferably0.5 to 5 percent by weight.

In case the content of the monomer B component is lower than the abovementioned range, the hot waterresistance of the obtained fibers andfilms can not be improved to any desired degree. On the contrary, incase it is higher than the above mentioned range, the elongation in thedry state of the obtained fibers and films is reduced and the materialslose their softness.

In regard to the protein to be used in the present in-, vention,particularly preferable are natural proteins such as cow milk casein,yeast protein, gelatin, corn protein and soybean protein. In addition,there can be used modified proteins such as cyanoethylated protein andcarbamylethylated protein or synthetic proteins.

It is preferable that the content of the protein in the resultingacrylic copolymer is 5 to 50 percent, more preferably 20-40 percent byweight. In case the content of the protein is lower than the abovementioned range, fibers high in the-hot water-resistance and dyeabilityand having a silky hand and films high in the dyeability can not beobtained. On the contrary, in case it is higher than the above mentionedrange, the toughness of the obtained fibers and films is reduced.

In carrying out the-polymerization it is preferable to use an acidicmedium of a pH of 6 or less, preferably a pH of 4 or less.

In case the polymerization is conducted in an acidic medium,substantially no cross-linking reaction proceeds during thepolymerization reaction and therefore av polymer solution stable inviscosity is obtained. On the other hand, in case the polymerization isconducted in a neutral or alkaline medium, a cross-linking reactionquickly proceeds simultaneously with the polymerization reaction and theviscosity of the polymerization system increases so that the system gelsand becomes unuseful as a solution for forming fibers and films in somecases. It is therefore recommended to conduct the polymerization in anacidic medium. Thus, in the present invention, it is-most preferable touse such medium showing itself an acidity as, for example, aconcentrated aqueous solution of zinc chloride. However, anymedium'whichis inherently neutral or basic can be also used by adjustingthepHto bein the acidic range by adding an acid.

Preferable media which can be used in the polymerization of the presentinvention are, for example, a concentrated aqueous solution of zincchloride, aqueous solution of nitric-acid,an aqueous solution of:nitratecontaining nitric acid,-an aqueous solution of perchloric acid,an aqueous solution of athiocyanate adjusted to be acidic, dimethylsulfoxide adjusted to be acidic, ethylene carbonate or anaqueoussolution of ethylene carbonate adjusted to'be acidic, an aqueoussolution of formic acid, a concentrated aqueous solution of ureaadjusted to be acidic, anaqueous system adjusted to be acidic, and amixture of any two or more of the above mentioned media. I

Except above, such other polymerization conditions as the monomerconcentration, catalyst, temperature and time maybe those known, per-se,in the art of polymerization or copolymerization, depending upon theparticular medium. ln this connection, reference may be made, forexample, to U.S. l? a t. No. 3,104,l54.

" Typical examples wherein the polymerization is conducted in aconcentrated aqueous solution of zinc chloride and dimethyl sulfoxideshall be described as follows. It is preferable that the concentratedaqueous solution contains 40 percent by weight to the saturation of zincchloride. If a second such substance as sodium chloride is to be addedto the solution, the amount of such second'substance is preferably inthe range of to 20 by weight.

The total concentration of the vinyl monomeric material, monomer Aprotein and/or monomer B to be added and dissolved into saidconcentrated aqueous solution of zinc chloride is preferably 3 to 40percent by weight.

In case the monomer B contains an amino group, imino group, pyridylgroup, pyrazinyl group or quinolyl group, it is preferable that saidmonomer B is added in the form of a hydrochloride.

For the polymerization catalyst may be used known radical polymerizationinitiators soluble in the concentrated aqueous solution of zincchloride, such as azobisisobutylonitrile, ammonium persulfate, potassiumpersulfate or hydrogen peroxide. The catalyst may also be a redoxcatalyst system in which is simultaneously used such reducing agents assodium sulfite, acidic sodium sulfi te, sodium thiosulfate or a ferroussalt. Further, the polymerization may also be conducted under theirradiation of radioactive rays such as, for example, gamma rays of Coor a light irradiation.

The polymerization temperature is 0 to 60C. The polymerization time maybe less than 40 hours.

In case dimethyl sulfoxideis used as a medium, it should be adjusted tobe acidic by adding an organic acid or inorganic acid before initiatingthe polymerization. Preferably, the amount of the acid to be added isless than percent by weight of the dimethyl sulfoxide. The vinylmonomeric material and protein and/or monomer B and/or protein may beadded and dissolved before the dimethyl sulfoxide is adjusted to beacidic but it is preferable, in preventing the gelling of thepolymerization system, to add the monomer A after the dimethyl sulfoxidehas been adjusted to be acidic. It is necessary that soybean proteinwhich is hardly soluble in dimethyl sulfoxide at the normal temperatureshould be dissolved at an elevated temperature such as 100 to 150C. Itis preferable that the total concentration of the vinyl monomermaterial, monomer A and protein and/or monomer B be 3 to 40 percent byweight of the dimethyl sulfoxide. For the polymerizing catalyst may beused radical polymerization initiators soluble in dimethyl sulfoxide,such as azobisisobutylonitrile or ammonium persulfate. Further, it maybe a redox polymerization in which a proper reducing agent issimultaneously used. Further, it is also possible to conduct thepolymerization with such radioactive rays as, for example, gamma rays ofCo or a light-irradiation. The polymerization temperature is 0 to 100C.and the polymerization time may be less than 50 hours.

The acrylic polymer solution obtained by the polymerization in a properacidic medium, as mentioned above, can be used for forming fibers andfilms. It is also possible to pour the solution into a nonsolvent forsaid polymer so that the polymer is precipitated and separated, washed,dehydrated and then dissolved into a proper acidic solvent such as, forexample, a concentrated aqueous solution of zinc chloride, dimethylsulfoxide adjusted to be. acidic, dimethyl formamide adjusted to beacidic or concentrated nitric acid. in the latter case, it is preferableto use washing water which has been adjusted to be acidic and at acomparatively low temperature, preferably below 30C. ln such case, thewashed and dehydrated polymer can be stably stored as it is in a wetstate for a considerably long time.

The acidic polymer solution is then extruded in the form of filament orfilm into an acidic or neutral coagulating bath or into a hot gaseousatmosphere such as hot air.

Fibers and films can be formed from the polymer solution by any wellknown method. For example, in the case of forming fibers by awet-spinning method from a concentrated aqueous solution of zincchloride of the acrylic polymer, the spinning solution is first filteredand deaerated and is then extruded through a spinnerette into an aqueoussolution of 5 to 33 percent by weight of zinc chloride so as tocoagulate the extruded filaments. The filaments are then waterwashed toremove zinc chloride and other materials deposited on them, are thenstretched in a wet heated medium such as steam, hot water or a hot bz 1th containing such salt as, for example, sodium sulfate and are driedand wound up.

In case an acidic dimethyl sulfoxide solution of the polymer is to beused as a spinning solution, there can be used a neutral dimethylsulfoxide-water mixed solution or n-butanol for the coagulating bath. Itis desirable to add an acid to such coagulating bath so as to be acidic.

In the case of forming a film, the acidic polymer solution is extrudedin the form of a film into an acidic or neutral coagulating bath or intoa hot atmosphere through a slit used of the spinnerette and the film iswashed with water and thermally stretched.

The filaments or films extruded into the acidic or neutral coagulatingbath or into a hot atmosphere contain an acidic substance having comefrom the original acidic polymer solution and/or the acidic coagulatingbath. After the formation of the fibers (filaments) or films,cross-linking reaction proceeds when the acidic substance is removede.g., by washing. The intermolecular cross-linking proceeds slowly atthe room or normal temperature, but proceeds rapidly at a highertemperature such as 50C. or higher, particularly at C. or higher.

It is preferable to stretch the formed fibers or films in order toimprove the mechanical properties. However, it is difficult to effectthe stretching after the cross-linking has considerably proceeded.Therefore, in this invention, it is preferable that the stretching isconducted while the cross-linking has not yet proceeded or has proceededonly to a very small extent, and that the cross-linking is substantiallyproceeded during or after the stretching. Thus, for example, the formedfilaments or films are stretched before the above mentioned acidicsubstance thereon is removed or while the said acidic substance is beingremoved. Alternatively, the acidic substance is first removed, andimmediately thereafter or after travelling in an air of the normaltemperature for a very short period of time, the filaments'or films arestretched. In order to complete the inter-molecular cross-linkingreaction, it is preferable to heat the filaments or films, during orafter formed due to the reaction of the halogenated striazinyl group orhalogenated pyrimidinyl group in the shaped article with the activehydrogen-containing group in the protein or/and the group containingactive 1 hydrogen, group capable of forming active hydrogen,

pyridyl group, pyrazinyl group or quinolyl group in the monomer B,within the fibers or films. Further, in the present invention, thehalogeno-s-triazinyl group or halogenopyrimidinyl group in the monomer Acomponent shows no reactivity in an acidic medium so that thecross-linking reaction does not substantially proceed during thepolymerizing reaction and up to the formation of the fibers or films.Therefore, the viscosity of the poly n er s9l utign is very stable foralong time dichloro-s-triazine (referred to as AAT). While the solutionwas kept at a temperature of 10C. and was being slowly stirred, 125parts of an aqueous solution of 60 percent zinc chloride containing 1.0percent ammonium persulfate and 250 parts of an aqueous solution of 60percent zinc chloride containing 1.0 percent sodium sulfite were addedto the solution. The polymerization was conducted under stirring at 10C.for 2 hours. The viscosity of the resulting polymer solution was 250poises at C. The polymerization conversion rate was 48.8 percent (No.1).

The same procedures were repeated except that AAT was added in an amountof 3.0 percent on the total amount of the monomers (No. 2) and that AATwas not added (No.3). g M NH Each of the polymer solutions thus obtainedwas filtered and deaerated, and then extruded through a spinnerette intoan aqueous solution of 28 percent zinc chloride kept at 2 to 0C. Theformed coagulated filaments were washed with water and stretched 15times the length in steam at 120C. to obtain fibers of a silky luster.The properties, dry and wet, of the fibers are shown in Table 1. Theirload-elongation curves in hot aters? QQYQarsshawa.b.5194:.

Table l Dry state n Wet state Initial Initial No. modulus modulusStrength Elongaof elas- Strength Elongaof elas- (g./d.) tion ticity(g./d.) tion ticity (gJ -l (g -l l 4.41 14.8 61.8 3.80 15.5 43.8 2 4.5914.0 72.5 4.00 15.0 47.9 3.40 16.2 37.3

Once such inter-molecular cross-linkage has been formed in the fibersand films, they do not dissolve again into the originalsolvent.

As compared with conventional acrylic fibers and films, the fibers andfilms produced by the present invention are higher in the strength whendry and wet, and are remarkably superior, particularly in suchproperties as the strength and elongation in hot water. Therefore, thefibers produced by the present invention, or their woven and knittedfabrics, and the films produced by the present invention are very highin the dimensional stability in a wet hot processing step such asdyeing. Particularly the protein-acrylonitrile graftcopolymer fibersproduced by the present invention have a silky luster and a soft elegantpeculiar hand.

The present invention will be explained in more detail by the followingexamples wherein all parts and percentages are by weight unlessotherwise specified.

EXAMPLE 1 Fifty parts of cow milk protein were dissolved in 1,940 partsof an aqueous solution of 60 percent zinc chloride. To this solutionwere added 123.75 parts of acrylonitrile (hereinafter referred to as AN)and 1.25 parts (corresponding to 1.0 percent on the total As apparentfrom Table 1, as compared with the control fibers (No. 3), the fibers(Nos. 1 and 2) of the invention were higher in the strength and initialmodulus of elasticity. As shown in FIG. 1, the fibers of this invention(Nos. 1 and 2) are remarkably superior particularly in strength andelongation in hot water.

EXAMPLE 2 Fifty parts of gelatin were dissolved in 2,000 parts of apercent aqueous solution of zinc chloride. To this solution were added115 parts of AN, 6 parts of methyl methacrylate and 3.75 parts of2-(p-vinyl anilino)-4,6- dichloropyrimidine (referred to as VAP). Thenthe solution was irradiated with gamma rays of 100 curies of Co at anintensity of 1.0 X 10 r./hr. at 30C. for 3 hours to effect thepolymerization. There was obtained a polymer solution (No. 5) with apolymerization conversion rate of 99.3 percent and a viscosity of 290poises at 30C.

The same procedure was repeated except that VAP was not added to obtaina polymer solution (No. 5).

Each of the polymer solutions was formed into filaments which werestretched under the same conditions as in Example 1 to obtain fibershaving a silky luster. The properties of the fibers thus obtained areshown in a u t of vtheJuana" 95 .1...91L2521113 m 60 Table Table 2 I inhot water Dry state Wet state at C.

Elonga- Elonga- Elonga- No. Strength Strength Strength tion tion tion(g./d.) (g /d.) (g.ld.)

As evident from Table 2, as compared with the coning to 1.0 percent onthe total weight of the monomers) trol fibers (No. the fibers (No. 4) ofthe present inand 0.75 part of ammonium persulfate were added to ventionwere higher in the strength both in dry and wet the solution. Thepolymerization was conducted at state and were remarkably superiorparticularly in the 30C. under a reduced pressure for 12 hours to obtainstrength and elongation and in the dimensional stability 5 a polymersolution (No. 8) of a polymerization converin hot water. sion rate of94.8 percent.

The same procedures were repeated except that EXAMPLE 3 AAT was added inan amount of 3.0 percent on the Fifty parts of soybean protein weredissolved in 1,940 total weight of the monomers (No. 9) and that. as aparts of an aqueous solution containing 55 percent zinc l 0 c0n t rol noAAT was added (No. chloride and 5 percent s odiu r n chloride To thissolu: Each of the three polymer solutions thus obtained tion were added1 l 5parts of AN, 6.25 parts of acrylwas extruded through a spinneretteinto an aqueous soamide (referred to as AAM hereinafter) and 3.75 partslution of 50 percent dimethyl sulfoxide of a pH adof2-amino-4-allyloxy-6-chloro-s-triazine (hereinafter justed to 3.51 withacetic acid. The formed filaments referred to as AAOT). While thesolution was kpt at were well. washed with water and were stretched l38C. and slowly stirred, 125 parts of an aqueous solutimes the length inhot water at 90C. to obtain white tion of 60 percent zinc chloridecontaining 1.0 percent fibers of a silky luster. The properties of thefibers are atn 9 1293 993 2 t pt na s 39.- ws nT b .43..

TABLE 4 ln hot water Dry state Wet state at 90C.

Initial Initial Elongamodulus of Elongamodulus of Elonga- No. Strengthtion elasticity Strength tion elasticity Strength tion (g./d.) (g-/ (g-/(g (gl -l lution of 60 percent zinc chloride containing 1.0 per-- Asevident from Table 4, as compared with the concent sodium sulfite wereadded to the solution and the trol fibers (No. 10), the fibers (Nos. 8and 9) of the inpolymerization was proceeded under stirring for 3vention were higher in the strength and initial modulus hours to obtaina polymer solution (No. 6) of a polyof elasticity both in dry and wet,and were remarkably merization conversion rate of 96.5 prercent and avissuperior particularly in strength and elongation in hot cosity of 215poises at 30C. water at 90C.

The same procedure was repeated except that AAOT was not added to obtaina polymer solution (No. 7). EXAMPLE 5 Each of these polymer solutionswere extruded Twenty-two and half parts of dried gelatin were disthrougha spinnerette into an aqueous coagulating bath 40 persed and heated at120C. to be dissolved in 277.5 containing 21 percent zinc chloride and 7percent soparts of anhydrous dimethyl sulfoxide. A small amount diumchloride. The formed filaments were treated in of concentratedhydrochloric acid was added to the sothe same manner as in Example 1 toobtain fibers havlution to adjust the pH to about 3.0. To this solutioning a silky luster. The properties of the fibers thus obwere added 47parts of acrylonitrile, 1.5 parts of methyl .t n ars hswn 9133 219 2- Im.l ha[Y.. 2L l.-. par of ..2(pn Table 3 In hot water Dry state Wetstate at 90C.

No. Elonga- Elonga- Elonga- Strength Strength Strength um um tion (g-l J(g-/ (g-/ As evident from TabTe 66515515055 the con dichloro-pyrimidine(hereinafter referred to as VAP).

trol fibers (No. 7), the fibers (No. 6) of the invention To thissolution was further added 0.75 part of were higher in the strength bothin dry and wet, and azobisisobutylonitrile. The polymerization wasconwere remarkably superior particularly in strength and ducted at 50 C.under a reduced pressure for 24 hours. elongation in hot water at 90C. IThe polymerization conversion rate in this example was 93.4 percent (No.11).

EXAMPLE 4 For comparison, the same procedure was repeated Twenty-two anda half parts of dried cow milk proexcept that VAP was not added toobtain a control tein were added and dissolved into 277.5 parts ofanhypolymer solution (No. 12).

drous dimethyl sulfoxide. A small amount of acetic acid Each of thesepolymer solutions was formed into filawas added t0 the solution toadjust the pH to about 3.5. ments under the same conditions as inExample 4110 ch- Then 49.5 parts ofAlfl, 0. Pj lLQLAA TLcorrespond- 7tain fibershaving a silky luster. The properties of the 13 14 fibersthus-obtained are shown in Table The monomer compositions were as inTable 7.

Table 5 In hot water Dry state Wet state at 90C.

Elonga- Elonga- Elonga- Nos. Strength Strength Strength t1on tion tionlgJ -l (g-/ (gJ As evident from Table 5, as compared wit lithe c on- I A"mm Table 7 trol fibers (No. 12), the fibers (No. ll) of the presentinvention were higher in the strength both in dry and 15 No. AN MA AATAA TOlill wet state and were remarkably superior particularly in thestrength and elongation in hot water at 90C. :2 35% 212 g g :38 17 92.154.85 3 100 EXAMPLE 6 18 95 0 0 100 Twenty-two and a half parts of driedsoybean protein 20 were dispersed and heated at 120C. to dissolve in277.5 parts of anhydrous dimethyl sulfoxide. Then formic acid was addedto the solution to adjust the pH to 3.0. To this solution were added 47parts of acryloni- I v trile, 1.5 parts of vinyl acetate and 1.5 partsof 2- 25 to Paris of an P solutlon of 60 Percent Zmcaminol4-allyloxy-6-s-triazine (hereinafter referred to L Q k at m thecase of 15 to 17 or as AAOT). To this solution was further added 0.75part m h case 9 Parts of an aqua of ammonium persulfate Thepolymerization was com ous solution of zinc chlorlde containlng 1.67percent ducted at 30C. under a reduced pressure for 18 hours. SoldiumSulfite and 80 Parts of an aqueous Solution of The polymerizationconversion rate in this example was 30 60 R m Zinc chloride vcpontainingfi 963 percent (N0; mon1um persulfate were added to the solut1on understirring. Further, after minutes, parts of the same except that AAOT wasnot added, to obtain a control Solution of ammonium Persulfate inpolymer Solution 14). chlorlde were added thereto and the polymer1zat1onEach of these two polymer solutions was formed into 35 was Conductedwith Stirring for 2 hours- The P y As evident from Table 7, the ratio ofAN/MA in Nos. 1 to 4 was fixed at 95/5.

One hundred parts of the total monomers were added For comparison, thesame procedure was repeated fibers under the same conditions as inExample 4 to obsolgltion was a d p tain fibers of a silky luster. Theproperties of the fibers In y case the P Y 'F P converslon Tate thusobtained are shown in Table 6. I Q 99 to 1.99, nets n ThQy icQgy at was00 Table 6 In hot water Dry state Wet state at 90C.

No. Strength Elonga- Strength Elonga- Strength Elonga- (g./d.) tion(g./d.) tion .ld.) tion As evident from Table 6, as compared with thecon- 50 poises in Nos. 15,-17 and 18 and 250'poises in No. 16.

trol fibers (No. 14), the fibers (No. 13) of the present Each of thesepolymer solutions was extruded invention were higher in the strength,lower in the elonthrough a spinnerette into an aqueous solution of 28gation and higher in the dimensional stability particupercent zincchloride. The formed filaments were larly in hot water. washed withwater and then stretched 15 times the length in boiling water at 100C.The properties of the EXAMPLE 7 fibers, in the dry and wetstates, areshown in Table 8 5 3 and their load-elongation curves in hot water at90C.

By usmg AN, AAT, methyl acrylate (hereinafter reare shown in FIG ferredto as MA) and allylamine (hereinafter referred to as AA) in variousproportions, the polymerization Table 8 was conducted at a total monomerconcentration of 8 Dry Wet ercent b wei ht in an a ueous solution of 60ercent I z inc ChlOZidfi Nos. 15 ai id l6). in this examp ie, AA 52 25325,253 2'53? was used in the form of a hydrochloride.

For comparision, the same procedure was repeated :2 2:32 2:1? exceptthat no AAT was used (N0. 17) and that neither 17 3.13 25.2 2.50 28.9

of AAT and AA were used (No. 18). a 18 Table in hot water Dry 7 Wet at90C.

Elonga- Elonga- Elonga- No. Strength tion Strength tion Strengt tion(g-/ (ll-I (B As evident from Table 8, as compared with the AN-MA 10 Asevident from Table 10, as compared with the concopolymer fibers (No.18), the copolymer fibers (No. 18), the copolymer fibers (No. 17) inwhich AA was added but AATT was not added were lower in the strength andhigher in the elongation. On the other hand, due to the inter-molecularcross-linkage at the time of the thermostretching, the copolymer fibers(Nos. and 16) of the present invention obtained by using both AA and AAThigher in the strength, lower tially dissolved.

trol fibers (No. 21), the fibers (Nos. 19 and 20) of the presentinvention were higher in the strength and smaller in the elongation andwere remarkably superior particularly in the strength and elongation inhot water at 90C.

EXAMPLE 9 By using AN, MA, AAT and allyl alcohol (hereinafter referredto as AOH) as monomers in various proportions, the polymerization w a sconducted at a total monomer concentration of 8 percent by weight in anaqueous solution of 60 percent zinc chloride at 15C. The polymerizingcatalyst and other polymerizing conditions were the same as in Example 7(but the polymerizing temperature in No. 24 was 20C. The monomercompositions, polymerization conversion rates and the viscosities(poises at C.) of the polymer ql swere asshoy in Table 1.1-.

EXAMPLE 8 With the monomers in various proportions as in Table 9, thepolymerization was conducted in the same manner as in Example 7 in anaqueous solution of 60 percent zinc chloride at 15C. The viscosity(centipoises at 30C.) of the thus obtained polymer solution is alsogiven in Table 9.

Each of the polymer solutions were deaerated and was then extrudedthrough a spinnerette into an aqueous solution of 28 percent zincchloride. The formed filaments were washed with water, stretched 10times the length in a glycerin bath at 120C. and were then dried. Theproperties of the fibers are shown in Table 12.

Table 12 In hot water Dry Wet at 90C.

Elonga- Elonga- Elonga- Nos. Strength Strength Strength tion tion tion(g./d.) (g- (gm) Table 9 As evident from Table 12, as compared with thecontrol fibers (Nos. 23 and 24), the fibers (N0. 22) of the No. AN AATAA (AA Tot 5 Viscosity present invention were superior particularly inthe of P y strength and elongation vin hot water at C. chloride monomerssolut1on mow 19 96 1 3 4.9) 100 360 EXAMPLE 10 2o 94 3 3 4.9 100 310 121 87 0 3 1 100 5 By using AN, MA, AAT and 4-v1nyl pyr1d1ne (herein-Each of the polymer solutions was deaerated and then extruded through aspinnerette into an aqueous solution of 28 percent zinc chloride. Theformed coagulated filaments were washed with water and then stretched 12times the length in boiling water and were then dried. The properties ofthe fibers thus obtained" after referred to as VP) as monomers invarious proportions, the polymerization was conducted at a total monomerconcentration of 8 percent weight in an aqueous solution of 60 percentzinc chloride at a polymerizing temperature of 18C. in the case of No.25 and at 20C. in the case of No. 26. The catalyst and other conditionswere the same as in Example 7. The monomer compositions and theviscosities (poises at 30C.) of the polymer solutions were as shown inTable EXAMPLE 1 1 1 o M. I By using AN, MA, 2-allylamino-4,6-dichloro-Table 13 Viscosity No. AN MA AAT VP(VP HCI) Total of of polymer monomerssolution pyrimidine (referred to as AAP) and AA as monomers in variousproportions the polymerization was conducted at C. for No. 27 and at C.for No. 28 in an aqueous solution of percent zinc chloride and otherwiseunder the same conditions as in Example 7. The monomer compositions andthe viscosity (poises at Each of the polymer solutions was deaerated andwas then extruded through a spinnerette into an aqueous solution of 28percent zinc chloride. The formed fila ments were washed with water,then stretched 10 times the length in a glycerin bath at 120C. and weredried. 20

Table 14 The properties of the fibers thus obtained are shown in 3530C.) of the obtained polymer solutions were as Table 14. 7 shown inTable 15.

Table 15 Viscosity No. AN MA AAP AA (AA HCl) Total of of polymerMonomers solution As evident from Table 14, as compared with the con-Each of the polymer solutions was spun and the filatrol fibers (No. 26),the fibers (No. 25) of the present ments were stretched and dried in thesame manner as invention were superior particularly in strength and inExample 7. The properties of the fibers are shown in elongation in hotwater .at 90C. Table 16.

Table 16 ln hot water Dry Wet at 90C.

Elonga- Elonga- Elonga- No. Strength tion Strength tion Strength tion(g-/ (g-/ (g-/ EXAMPLE 12 By using AN, AAM, AAOT and AA in variousproportions the polymerization was conducted in the same manner as inExample 7 in an aqueous solution of 60 percent zinc chloride. Themonomer compositions em- Thus, 100 parts of the total monomers (AA wasadded in the form of a hydrochloride) were added into 1,040 parts ofdeoxygenated water of'a pH of 1.5 kept at 35C. for N0. 32 and at 40C.for No. 33. Then. 5.8 parts of an aqueous solution of 12 percent sodiumsulfite and 5.8 parts of an aqueous solution of 8 percent ammoniumpersulfate were further added thereto with stirring in a nitrogenatmosphere and the polymerization was conducted for 4 hours. The formedpolymer precipitate was separated, washed several times with l P y QTable i h case of N lN hydrochloric acid, and once with water and dehy-29 (P165611t mvemlon) the polymerizatlon converslon drated with acentrifugal separator. The polymer rate was 99.6 percent and theV1SCOS11IyOf the resulting (moisture content f 30 percent) was directlyadded P y Solution was 260 1301595 at 30 into a solvent consisting of 55percent nitric acid,

Table 7 15 percent zinc nitrateand percent water so as to produce apolymer concentration of 13 percent by weight. Nu AN AAM AAOT AA (AA ChThe mixture was stirred at 10C. to dissolve the polymer. The resultmgpolymer solution was deaerated 29 893 3 3 (4-9) 100 while being kept at10C. and was extruded through a 92.15 4.85 0 3 4.9 100 3! 95 5 0 0 mo 20spmnerette into an aqueous solution of percent n1- tric acid at 10C. Theformed coagulated filaments The properties f the fibers obtained f thepoly were washed with water, stretched 7 times their length metSolutions in the same manner as in Example 9 arev in boiling water andwere dried. The properties of the shown in Table 18. tmedfibe aru n Tale Table 18 in hot water Dry Wet at 90C.

Elonga- Elonga- Elonga- No Strength tion Strength tion Strength tion(EM) (g-M) (g-/ Table 20 in the hot water Dry Wet at 90C.

Elonga- Elonga- Elonga- No. Strength tion reng tion Strength tion (g-/(g-/ (g As evident from Table 18, as compared with the As evident fromTable 20, even in case the polymercontrol fibers (Nos. 30 and 31), thefibers (N0. 29) of ization was conducted in a nonuniform system, ascomthe present invention were superior particularly in pared with thecontrol fibers (No. 33), the fibers (N0. the strength and elongation inhot water at 90C. 32) of the present invention were superior in the th 1a i h t 9 EXAMPLE 13 streng and e ong tron n 0t water a 0 C By usingvarious monomers as shown in Table 19, the EXAMPLE l4 polymerization wasconducted in a non-uniform sys- With the same monomers as in Example 13,the polytem at a total monomer concentration of 8.7 percent bymerization was conducted at a total monomer concenweight in dexoygenatedwater adjusted to a pH of 1.5 tration of about 20 percent by weight indimethyl sulwith sulfuric acid. foxide at a temperature of 40C. adjustedto a pH of 1.2

Table 19 With SUlflll'iC acid.

Thus 100 parts of the total monomers were added to N0. AN MA AAT AA (AAHCU Tom 395 parts of dimethyl sulfox de ofa pH of 1.2. Further, 0.3 partof azobisisobutylomtrile and 0.1 to 0.3 part of 5 2183) :88 dodecylmercaptan were added thereto and the polymerization was conducted withstirring at 45C. for 40 21, hours in a nitrogen atmosphere. Theresulting polymer solution was deaerated and was then extruded through aspinnerette into an aqueous solution of 82 percent dimethyl sulfoxide at40C. The formed coagulated fila- T l 22 ments were stretched 7 timestheir length in a glycerin o bath at 120 C., washed well wlth water,then passed as AN MA AAT AA (AA HCI) Tum] tens1oned through a bollmgwater bath'at 100C. and finally dried. The Properties of the obtainedfibers are 3; 31- g 2 shown in Table 21. i

Table 21 In hot water Dry Wet at 90C.

Elonga- Elonga- Elonga- No Strength tion Strength tion Strength tion(g./d.) (g-/ (g-/ Table 23 in hot water Dry Wet at 90C.

Elonga- Elonga- Elonga- No. Strength tion Strength tion Strength tion(gJ -l (g-/ (g-/ As evident from Table 21, as compared with the con- Asevident from Table 23, as compared with the control fibers (No. 35), thefibers of the present invention trol fibers (No. 37), the fibers (No.36) of the present were superior particularly in the strength andelonga- 35 invention were remarkably superior particularly in the tionin hot water at 90C. strength and elongation in hot water at 90C.

EXAMPLE 15 h EXAMPLE Y using AN, MA, 0 and AA as moflofnefsin Each ofthe polymers obtained in Example 13 was ious proportions and usmgazoisobutylomtnle asacata- 40 dded and dissolved with stirring intodimethyl acetyst, the polymerizatio was Conducted at a total m amideadjusted to a pH of 1.2 with sulfuric acid, so as mer concentration of14.5 percent by weight in an to produce apolymer concentration of 20percent. The aqueous solution of 94 percent ethylene carbonate 1npolymer solution was filtered, deaerated and then exa nitrogenatmosphere at C. for 20 hours. The retruded through a spinnerette intoan aqueous solution sulting polymer solution was vof a viscosity of 705poises 45 of percent dimethyl acetamideat 20C. The formed at 50C. and apolymer conversion rate of 89.5 percent filaments were washed withwater, then stretched 6 (N0. 36). i 4 times their length in boilingwater at to C. and For comparison, the same procedure was repeated weredried. The properties of the obtained fibers are except that AAT and AAwere not added to obtain a shown in Table 24. 7

Table 24 in hot water Dry Wet at 90C.

Elonga- Elonga- Elonga- No. Strength tion Strength tion Strength tion(g-/ (g-l (g-/ polymer solution (No. 37) of a viscosity of 730 poises Asevident from Table 24, as compared with the conand a polymerizationconversion rate of 88.0 percent. trol fibers (No. 39), the fibers (No.38) of the present 8 Each of the polymer solutions was deaerated and wasinvention were remarkably superior particularly in the then extrudedthrough a spinnerette into an aqueous 65 strength and elongation in hotwater at 90C.

coagulating bath at 30C., adjusted to a pH of 1.8 with hydrochloricacid. The formed filaments were water-,

washed then stretched 7 times their length in boiling ate andwedriedlhemommsr qmpqtio iami ployed are shown in Table 22 and theproperties of the obtained fibers are shown in Table 23.

EXAMPLE 17 Four parts of soybean protein were dissolved in parts offormic acid. Then 15.5 parts of AN, 0.5 part of AAT and 0.6 part ofa,a'-azoisobutylonitrile were added thereto and the mixture waspolymerized at 60C. under a reduced pressure for 6 hours (No. 40). Then,the resulting reaction mixture was put into 500 24 As evident from Table26, as compared with the control fibers (No. 43), the fibers (No. 42) ofpresent invention were remarkably superior particularly in theirstrength and elongation in hot water at 90C.

parts of water and was dehydrated with a centrifugal 5 separator toobtain 23.4 parts of a hydrous polymer of a moisture content of 30percent. This hydrous poly- EXAMPLE l9 7 mer was added and dissolvedwith stirring into an aqueous solution of 60 percent zinc chloride toobtain a solution of a polymer concentration of 8 percent. The polymersolution was filtered and deaerated and was then extruded through aspinnerette into an aqueous solution of 28 percent zinc chloride at C.The formed filaments were washed with water, then stretched 15 timestheir length in steam at 120C. and were dried to obtain fibers having asilky luster.

The same procedure was repeated except that AAT was not added (No. 41).

The properties of the fibers thus obtained are shown Five parts of cornprotein were added to 80 parts of dimethyl formamide adjusted to a pH of2.0 with phosphoric acid and were dissolved therein with stirring at theroom temperature. Then, to this solution were added 14.85 parts of ANand 0.15 part of AAT and, as catalysts, 0.006 part of cupric nitrate and0.225 part of potassium persulfate. The mixture was polymerized withstirring in a nitrogen gas current for hours (No.

cent.

Thesameprocedure was repeated except that AAT trol fibers (No. 41), thefibers (No. 40) of the present invention were remarkably superiorparticularly in theirstrength and elongation in hot water at 90C.

parts of an aqueous solution of 50 percent urea adjusted to a pH of 6.01with hydrochloric acid. To this solution were added 15.5 parts of AN,0.5 part of AAT 3 119) Pa 9 2194:azgi but qni rilshe 1 1 29 129 was 40polymerized at 60C. for 6 hours (No. 42). Then the polymer washed withwater adjusted to a pH of 6 and was dehydrated to obtain 21.7 parts of ahydrous polymer of a As evident from Table 25, as compared with the con-30 was added in an amount of3 .0 p ercent based on the total monomers(No. 45) and that no AAT was added 89-116):

Each of the three polymer solutions was extruded through a spinneretteinto a hot air spinning tube at 200 to 250C. and the formed filamentswere taken at a velocity of 1 l0 m./min. The filaments were thenstretched 5 times their length in hot water at 100C. and were dried toobtain fibers having a silky luster. The properties of the fibers thusobtained are shown in Table 27.

EXAMPLE 18 Four parts of cow milk casein were dissolved in 190 Table 27In hot water Dry Wet at 90C.

Elonga- V Elonga- No. Strength tion Strength tion Strength tion (g-/(g./ (g-/ As evident from Table 27, as compared with the control fibers(No. 46), the fibers (Nos. 44 and 45) of the present invention werehigher in the strength when dry and wet and remarkably superior,particularly in precipitate was centrifugally separated,

water content of 28 percent. The hydrous polymer was Strength and elongo in ot ater a 90C- processed in the same manner as in Example 17 toobtain fibers having a silky luster (No. 42). EXAMPLE 20 For comparison,the same procedure was repeated A Polymer Solution Obtained in the Samemanner as except that AAT was not added (No 43 in Example 1 was extrudedthrough a slit 1.5 mm. wide The properties of the fibers thus obtainedare shown f l l Into an aqueous Solution of 35 Percent in Table 26 v V znc chlor de at 0C. and was madeto slide down, while Table 26 In hotwater Dry Wet at C.

Elonga- Elonga- 151151195 i No. Strength tion Strength tion Strengthtion (gJ -l (sJ (g-/ 44). The polymerization conversion rate was 94.3perwater at 90C.

being slowly coagulated at a velocity of m./min., on a flatplate,inclined by degrees within coagulating bath. Then, the coagulatedfilm was transferred to a water-washing bath, and was then stretched 5times terial consisting mainly of acrylonitrile, (b) 0.03 to 10 percentby weight, based on the weight of the copolymer, of a polymerizableunsaturated monomer having a group selected from the class consisting ofhalogetheir length in one direction in hot water to obtain a 5 natedS-triazinyl groups of the general formula: stretched transparent film(No. 47).

1n the same manner films were prepared from the polymer wherein theamount of AAT was 3.0 percent based on the total amount of the monomers(No. 48) X1 and also from the polymer not containing AAT (NO. 10 I 49The physical properties in the stretching direction of N==K the filmsare shown in Table 28. X2

Table 28 Dry Wet in hot water at 90C.

Tensile Tensile Tensile No. strength Elongation strength Elongationstrength Elongation Shrinkage s/ s/ s-I As evident from Table 28, ascompared with the control film (No. 49), the films of the presentinvention (Nos. 47 and 48) were remarkably superior particularly in thestrength, elongation and shrinkage in hot EXAMPLE 21 Films were formedunder the same conditions as in Example except that polymer solutionsobtained in the same manner as in Example 7 were used. The physicalproperties of the films in the stretching direction are shown in Table29 wherein Nos. 50 to 53 correspond repsst ys m P ea--3551 in Tablelandhalogenated pyrimidinyl groups of the general formula:

wherein each of X and X is a halogen, hydrogen, alkyl group, aminogroup, hydroxyl group, mercapto group or carboxyl group, and wherein atleast one of X 1 and X must be a halogen, (c) 0.3-10 percent by weight,based on the weight of the copolyrner, of a polymeriz- As evident fromTable 29, as compared with the control films (Nos. 52 and 53), the filmsof the present invention (Nos. 50 and 51) were remarkably superiorparticularly in the strength, elongation and shrinkage in hot water at90C.

What is claimed is:

1. An acrylic fiber or film of a cross-linked copolymer consistingessentially of (a) avinyl monomeric maable unsaturated monomer componentcontaining an active hydrogen group selected from the class consistingof amino, imino, hydroxyl, glycidyl, pyrazinyl and quinolyl groups, saidcross-linking existing between the active hydrogen group of component(c) and the halogenated S-triazinyl group or halogenated pyrimidinyl 2232 of Component b

1. AN ARCYLIC FIBER OR FILM OF A CROSS-LINKED COPOLYMER CONSISTING ESSENTIALLY OF (A) A VINYL MONOMERIC MATERIAL CONSISTING MAINLY OF ACRYLONITRILE, (B) 0.03 TO 10 PERCENT BY WEIGHT, BASED ON THE WEIGHT OF THE COPOLYMER, OF A POLYMERIZABLE UNSATURATED MONOMER HAVING A GROUP SELECTED FROM THE CLASS CONSISTING OF HALOGENATED S-TRIAZINYL GROUPS OF THE GENERAL FORMULA: 